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Electrochimica Acta, Vol.41, No.14, 2329-2338, 1996
Electron and Ion Transfer-Reactions on Metal-Electrodes
An extended Anderson model is used as a unifying framework far both ion and electron transfer reactions. The model allows the construction of effective potential energy surfaces as functions of the solvent coordinates and the separation of the reactant from the electrode surface. For electron transfer the reaction coordinate is mainly in the direction of the solvent coordinates; for ion transfer the partial loss of the solvation sheath and the encompanying solvent displacement is the rate determining step, and the reaction coordinate is mainly determined by the separation from the metal surface. Further differences and similarities between the two types of reactions are discussed.